Regulating the Coordination Geometry and Oxidation State of Single‐Atom Fe Sites for Enhanced Oxygen Reduction Electrocatalysis

Abstract FeNC catalysts demonstrate remarkable activity and stability for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells and Zn–air batteries (ZABs). The local coordination of Fe single atoms in FeNC catalysts strongly impacts ORR activity. Herein, FeNC catalysts containing Fe single atoms sites with FeN 3 , FeN 4 , and FeN 5 coordinations are synthesized by carbonization of Fe‐rich polypyrrole precursors. The FeN 5 sites possess a higher Fe oxidation state (+2.62) than the FeN 3 (+2.23) and FeN 4 (+2.47) sites, and higher ORR activity. Density functional theory calculations verify that the FeN 5 coordination optimizes the adsorption and desorption of ORR intermediates, dramatically lowering the energy barrier for OH − desorption in the rate‐limiting ORR step. A primary ZAB constructed using the FeNC catalyst with FeN 5 sites demonstrates state‐of‐the‐art performance (an open circuit potential of 1.629 V, power density of 159 mW cm −2 ). Results confirm an intimate structure‐activity relationship between Fe coordination, Fe oxidation state, and ORR activity in FeNC catalysts.